CN1300003C - Autoclave control method for pressure oxidation of molybdenite - Google Patents
Autoclave control method for pressure oxidation of molybdenite Download PDFInfo
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- CN1300003C CN1300003C CNB018232434A CN01823243A CN1300003C CN 1300003 C CN1300003 C CN 1300003C CN B018232434 A CNB018232434 A CN B018232434A CN 01823243 A CN01823243 A CN 01823243A CN 1300003 C CN1300003 C CN 1300003C
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Abstract
The process chemistry during the oxidation of molybdenite concentrates in an oxygen pressure leach can be controlled by regulating the amount of ferric iron and excess sulfuric acid recycled as autoclave discharge slurry or filtrate to the autoclave feed. A computer model capable of predicting the concentration of soluble molybdenum in the autoclave discharge and based on the concentrate and recycle analyses was developed.
Description
Invention field
The present invention relates to the process chemistry of molybdenum glance enriched material high-pressure oxidation, specifically, relate to the method for the process chemistry of control and optimization molybdenum glance enriched material high-pressure oxidation.
Background of invention
Utilizing water law to extract molybdenum from the material that contains molybdenum glance has been similar 50 years research topic.Nineteen fifty-two, E.S.Usataya
1Reported the oxidizing reaction of molybdenum glance in the aqueous solution.He finds that in neutrality, acidity or weakly alkaline solution, degradation production is deposited on the molybdenum glance surface, can prevent the further oxidation of molybdenum glance.He finds that also highly basic and strong oxidizer can hinder the formation of protective layer.In basic solution, elevated temperature can be accelerated oxidation rate, but in acidic solution, temperature is elevated to until 60 ℃ still there is not what effect.
1962, a Japanese Patent
2Reported the hyperbaric oxygen oxidizing reaction (POX) of molybdenum glance.An embodiment of this patent has separated out the enriched material that contains Mo 55.5%, S 36.4% and Cu 4.4% under 200 ℃ and 200 atmospheric oxygen effects, solids content is 9%.The precipitate molybdic acid that forms in precipitation process is dissolved with ammonia, and with the form recovery of ammonium molybdate, reaction formula is as follows:
1971, AMAX was with similar reaction
3Obtained patent, but the temperature of selecting is higher than 80 ℃, pressure is greater than 3.5 normal atmosphere.In another AMAX patent
4In, in the molybdic acid forming process, constantly add in the alkaline hydrated oxide and the acid that generates, thereby make pH remain on 7-12.
1Usataya，E.S.，“Oxidation of molybdenite in water solutions”，Zapiski Vsesoyuz Mineral Obshschestva，v81，298-303(1952).
2Sada, Koji, " Extraction of molybdenum ", Japanese Patent 15.207 (' 62), transfer Awamura Mining Co., Ltd.
3Barry, people such as Henry F., " Aqueous phase oxidation of molybdenumdisulfide ", German Patent 2,043,874 (1971).
4Hallada, Callvin J. waits the people., " Conversion of molybdenum disulfide tomolybdenum oxide ", German Patent 2,045,308 (1971).
Mel ' nikov
5People such as, K.Ya.Shapiro in 1970
6Reported the high-pressure oxidation reaction of molybdenum glance in the presence of sulfuric acid in 1973.Shapiro infers that soluble molybdenum material is MoO
2SO
4The used oxidation enriched material of Mel ' nikov comprises 17% Mo and 15% Fe, and solids content is 16%, and temperature is 100 ℃.Shapiro is a solids content 9% to the condition that 47% Mo enriched material adopts, 225 ℃ of temperature, and oxygen pressure is lower than 10 normal atmosphere, and the reaction times is 3 hours.
Irkov in 1970
7One piece of paper reported molybdenum oxide in sulfuric acid respectively at the solubleness under 22,50,71 and 89 ℃.This paper shows that the solubleness of oxygen molybdenum reduces along with the rising of temperature, and acid concentration surpasses 20% to its influence.
Shapiro and Mel ' nikov
8The paper of delivering in 1975 has been reported about 1) pure molybdenum glance (99.5%MS
2), 2) high purity enriched material (47%Mo), 3) the POX disaggregate approach of low-purity Industrial products (16%Mo and 15%Fe).The condition of separating out is a solids content 9%, and temperature is lower than 160-225 ℃, oxygen superpressure 5-20 normal atmosphere, time 15-195 minute.
This paper has shown that temperature is to the influence of oxidation rate under 15 atmospheric superpressure oxygen.Oxidation rate was very fast when temperature surpassed 190 ℃.The oxygen superpressure was to the influence of oxidation when this paper had also disclosed 225 ℃.Oxidation rate directly is directly proportional with the oxygen superpressure.The paper author infers that the oxidation rate that influenced by temperature and oxygen superpressure has been controlled the meltage of molybdenum.
5Shapiro, K.Ya waits the people., " Sulfuric acid processing of oxidizedmolybdenum raw materials ", Nauk.Tr.Vses.Nauch.-Issled.Proekt.Inst.Tugoplavkikh Metal.Tverd.Splavov, 1970.
6Mel ' niko, people such as B.S.., " Oxidative water-autoclave leaching ofmolybdenum concentrate ", Nauchn Tr., Vses.Nauchno-Issled.Proektn.Inst. (1973) 14,251-157.
7Irkov，F.Ya，Palant，A.A.，and Reznichenko，V.A.，“Solubility ofanhydrous molybdenum(VI)oxide in aqueous solutions of sulfuric acid”，Russian Journal of Inorganic Chemistry，v 15，5，695-697(1970).
8Mel ' niko, B.S. and Shapiro, K.A., " Water-autoclave decomposition ofmolybdenuite raw material ", Protsessy Poluch.FafinirovaniyaTugoplavkikh Met. (1975) 113-120,253-260.
This paper has also been studied the influence that adds iron in the high purity molybdenum glance.Adding iron can greatly improve the oxidation rate of molybdenum glance.After adding iron, temperature reduces the influence of speed.Under the condition that iron exists, the molybdenum content in the solution reached peak value in the molybdenum glance oxidation near 60% o'clock, was reduced to then about the twice of molybdenum content when not adding iron.Paper author supposition has formed the assorted polygamy compound of molybdenum-iron in oxidising process, this title complex decomposes when acid concentration increases.Also might be that iron (ii) complexes decomposes when dissolved iron is oxidized to ferric iron.
This paper has also been studied the oxidation of low-purity (technical purity) enriched material, and temperature when the oxygen superpressure is lower than 15 normal atmosphere (150-225 ℃) is to the influence of solubleness, iron and the vitriolic concentration of oxidation rate, molybdenum.The paper data clearly illustrate that, produce enough sulfuric acid in enough pyrite/chalcopyrite oxidation, when beginning the oxidation of molybdenum glance, have an incubation period.Soluble iron reaches 8g/l greatly approximately, and sulfuric acid concentration approximately reaches before the 40g/l, and the quick oxidation of molybdenum glance does not take place.The paper data show that water can not get being generalized to the data of flow reactor as the batch test of precipitation agent.
Rothmann
9At, Bauer in 1980
10The patent that has obtained respectively about oxygen high pressure precipitation process in 1984 adds sulfur acid with molybdenum glance and reaches in the reaction mixture of 100g/l in this process.Separate out under 250-300 ℃, 10-20 normal atmosphere oxygen superpressure and carry out.
1986, Gock
11Obtained patent, the flotation agent that this reaction does not have complete oxidation to comprise about oxidation molybdenum glance (97.5%).This will make molybdenum remain soluble reduction valence state material, and not producing can sedimentary sexavalence material.Reaction conditions (pH is sour precipitation agent, 160-220 ℃, the oxygen superpressure of 0.2-0.6) does not show the control to reaction is how to prevent the complete oxidation of flotation agent.
9Rothmann, Hans W. and Bauer, Guenter, " Method of recovering molybdenumoxide ", German patent DE 2,830,394 (1980).
10Bauer, Guenter and Eckert, Joachim, " Recovery of molybdenum oxide ", German patent DE 3,128,921 (1983).
11Gock, Eberhard, " Pure molybdenum trioxide produced by way ofextraction of molybdenum from sulfate solutions ", German patent DE 843,443,806 (1986).
1998, Cyprus Amax
12A process is obtained patent, in this process, in the filtrate of last reaction, added molybdenum glance, be oxidized to 70%-95% then.Unreacted molybdenum glance reclaims from solid with froth-flotation method.Unreacted molybdenum glance and some debris are returned in the precipitating reactor and are circulated.Oxidizing condition is 175-225 ℃, 50-300psig oxygen superpressure.The flotation residue is that molybdenum oxide and/or molybdic acid also comprise a small amount of molybdenum glance, must roasting become molybdenum oxide before sale.Other raffinates in the autoclave reclaim rhenium and copper through handling.
Brassier and Pascal
13The forming process of Canadian Patent heteropoly compound when having studied the thick calcium molybdate of separating out with sulfuric acid precipitation.Data in this patent show, when the sulfuric acid that is lower than 0.5M (49g/l) with concentration carries out evolution reaction, obviously form assorted polyphosphate and silicate.When separating out with the sulfuric acid of 1M, the amount of heteropoly compound reduces by one more than the order of magnitude.Can infer from these data, must comprise enough free acids in the initial evolution reaction thing, to avoid to form the scope of the acid concentration of heteropoly compound.
From used for many years various technologies, condition and theory, can be clear that, also need the process chemistry that relates to oxidation molybdenum glance enriched material is fundamentally inquired into, so that control the chemical reaction of oxygen high pressure in separating out reliably, and after the reaction of prediction high-pressure oxidation, the concentration of the solvable molybdenum that exists in the slurries that autoclave is discharged.
Therefore, a target of the present invention provides one and separates out model, and it can predict the molybdenum glance enriched material after the high-pressure oxidation reaction, the concentration of the solvable molybdenum that exists in the slurries that autoclave is discharged.
Another target of the present invention provides the method for optimizing and control its process chemistry in the process of pressure oxidation of molybdenite enriched material.
Summary of the invention
By some embodiments of the present invention that describe below, can realize above-mentioned target of the present invention, and other targets and advantage.
12Sweetser, W.H. and Hill, L.N., " Process for autoclaving molybdenumsulfide, " United States Patent (USP) 5,804,151 (1998).
13Brassier, Cecile and Baron, Pascal: Canadian Patent 2,154,133 (1986), and French Patent 2,272,701. " Process for the recovery of molybdenum fromimpure calcium molybdate resulting from the treatment of uraniferousores ".
The invention provides one and separate out model, it can predict the amount of the solvable molybdenum that the molybdenum glance enriched material exists in the high-pressure oxidation reaction process, and the method for optimizing and control its process chemistry in autoclave in the high-pressure oxidation reaction of carrying out is provided.
Therefore, one aspect of the present invention provides a kind of method of pressure oxidation of molybdenite enriched material, and this method comprises:
A. form the water-soluble serous of described molybdenum glance enriched material;
B. heating described slurries arrives at least about 200 ℃;
C. with the atmosphere contact conditions that contains free oxygen under stir described slurries;
D. be at least about the described slurries of oxidation in the described atmosphere of 50p.s.i. at oxygen pressure;
E. predict dissolved molybdenum in the high-pressure oxidation process, comprising:
E1: the approximate concentration of prediction excess sulfuric acid;
E2: the approximate concentration of prediction dissolved iron;
F. in oxidation reaction process, regulate ferric iron concentration and excess sulfuric acid concentration;
G. produce thus and separate out slurries, surpass 99% molybdenum in the wherein said molybdenum glance enriched material approximately and obtain oxidation;
Wherein, adopt the concentration of the model prediction molybdenum glance enriched material solvable molybdenum behind high-pressure oxidation shown in the accompanying drawing 4, each meaning of parameters and method of calculation are as shown in Figure 4 in this model.
In a preferred embodiment, regulating step makes that ferric iron maintains higher concentration in the described slurries, in order to accelerate oxidizing reaction speed.
In a preferred embodiment, this method also comprises the described slurries of separating out of a part that produces in the step (g) is turned back to and form in the step (a).
In a preferred embodiment, the oxygen overpressure in the oxidation step is in about 80-120p.s.i. scope.
In another preferred embodiment, the temperature of heating steps is in about 210-220 ℃ scope.
In a preferred embodiment, prediction steps (e1) is by enriched material weight and analyzes the volume and the analysis that add circulate soln and calculate.
In another preferred embodiment, prediction steps (e1) also comprises: (1) carries out the initial calculation of excess sulfuric acid concentration; (2) concentration by the further calculation correction excess sulfuric acid of one or many compensating extra sedimentary molybdenum, thereby is improved initial calculation.
According to the present invention, can control the process chemistry of molybdenum glance enriched material high-pressure oxidation, finally separate out the recovery that the amount of ferric iron and excess sulfuric acid in the slurries promotes molybdenum by regulating.Oxidation kinetics is controlled by temperature used in the autoclave and oxygen superpressure.This model is predicted the concentration of solvable molybdenum based on used enriched material analysis, circulate soln analysis and serum density.Discover that good oxidation kinetics need be higher than 200 ℃ temperature and greater than the oxygen superpressure of 50psig.
This model can determine that molybdenum solubleness does not rely on the condition of molybdenum oxidizing reaction.Utilize computer model, the oxidation of molybdenum glance reaches and surpasses 99% level, is lower than 20% or to surpass 80% molybdenum be soluble and have in the final slurries that produce.The pyrite and the chalcopyrite that are present in the molybdenum glance enriched material have the copper material above 99% to dissolve, the iron substance dissolving of 60%-90%.Overwhelming majority iron substance can be with the form precipitation of iron molybdate.By separating out under the excessive greatly condition of acid, the amount of solvable silicon remains under the 100g/l.Most of rhenium, arsenic and phosphorus dissolving, and with separate out conditional independence.
To preferred implementation, comprise illustrative unrestricted embodiment by following, the description that modeling method and products therefrom are formed, other targets of the present invention, characteristics and advantage will be apparent.
Brief Description Of Drawings
Fig. 1 a is the graph of a relation of solvable molybdenum concentration and titration sulfuric acid concentration.
Fig. 1 b is the graph of a relation of solvable molybdenum concentration and ferric iron concentration.
Fig. 1 c is the graph of a relation of solvable molybdenum concentration and ferric iron and excess sulfuric acid concentration.
Fig. 2 a-2c is the solvable molybdenum concentration that exists with three kinds of different substancess and the graph of a relation of excess sulfuric acid concentration.
Fig. 3 be the excess sulfuric acid concentration calculated with in batches-long run test in the graph of a relation of titration sulfuric acid concentration of filtrate.
Fig. 4 is that solvable molybdenum concentration is set up behind high-pressure oxidation separates out model for prediction molybdenum glance enriched material.
Fig. 5 is the graph of a relation of the solvable molybdenum concentration of POX-of solvable molybdenum concentration of actual POX-and model prediction.
The preferred embodiment for the present invention
The laboratory carried out a series of high pressure separate out the experiment and collected enough statistic datas after, set up the model of separating out that can predict solvable molybdenum concentration.Experimental data shows, separates out temperature, time and oxygen superpressure the solubleness of molybdenum is had no significant effect.Influencing significant variable is the final acid and the concentration of iron.Fig. 1 a, 1b and 1c have shown the influence of these variablees to molybdenum solubleness.Among Fig. 1 a, demonstrate good dependency between the increase of the reduction of molybdenum solubleness and titration sulfuric acid value.Among Fig. 1 b, the increase of molybdenum solubleness and the increase of concentration of iron demonstrate good dependency.In Fig. 1 c, molybdenum solubleness and model (iron adds superacid concentration) demonstrate good match dependency (R
2=0.96).
The first step that makes up model is to determine to have which material in the lye, how to measure acid concentration.The sulfate concentration height of lye helps bisulfate ion negatively charged ion and metallic cation balance.Therefore, the supposition of this modeling method, iron and copper are with Fe (HSO
4)
3And Cu (HSO
4)
2The form dissolved.Russian scientist (Shapiro and Mel ' nikov) supposed once that solvable molybdenum material was MoO
2SO
4Fig. 2 a-2c has drawn with three kinds of material form [H
2MoO
4, MoO
2SO
4, MoO
2(HSO
4)
2] concentration and superacid graph of a relation of the solvable molybdenum that exists.These curves have only adopted the data of all good experiment of sulfide oxidation and metal balance.If supposition molybdenum material is MoO
2(HSO
4)
2, molybdenum concentration and excess acid demonstrate good match dependency, R
2Value is 0.81.
The control model is based on to the acid concentration of final (excessive) and the prediction of soluble iron concentration.Excess acid is defined as with the acid substance titration and with regard to bisulfate ion has carried out gauged titration acid number, adds any acid that titration process produces.The titration process that adopts in the laboratory study is from using Potassium Oxalate Solution titration aliquot sample to be measured.Positively charged ion and oxalate complexing discharge bisulfate ion then, so that use the potassium hydroxide titration.The drop reaction equation is as follows substantially:
When with KOH titration above-mentioned ion, react and be:
Therefore, each cupric ion is corresponding to two hydrogen sulfate ions in the titration, and each iron ion is corresponding to three hydrogen sulfate ions, and each molybdenum ion is corresponding to two hydrogen sulfate ions and two hydrogen ions.After Titrable acid being corrected to the hydrogen sulfate ion and hydrogen ion corresponding with copper, iron and molybdenum, remaining acid is " excess acid ".Fig. 3 shows that " excess acid " of titration sulfuric acid value and calculating has good dependency.
So just can set up an equation, add that from enriched material weight and species analysis the liquor capacity of recovery and species analysis predict superacid amount.The reaction of supposing is:
Other inorganic sulphides also react and form solvable hydrosulfate.In this case, lead might precipitate into vitriol.
Notice that none produces excessive acid in the above-mentioned reaction.In fact, chalcopyrite and pyrite are consumption acids.Under autoclave conditions, copper and iron substance dissolve rapidly, have some iron substances (15%-25%) to be precipitated as Fe subsequently
2O
3At last, some molybdenum material hydrolysis produce acid.Below be elementary precipitin reaction:
In case iron and/or molybdenum begin precipitation, excessive acid just increases sharply, and causes more molybdenum precipitation.The precipitation capacity of estimating iron is extremely important with the amount of sedimentary molybdenum for prediction.
Fig. 4 is the model of setting up for the solvable molybdenum concentration of prediction molybdenum glance enriched material behind high-pressure oxidation.The principle of this model is based upon to be calculated the second time of calculating the first time of estimating excess acid and carrying out and carrying out with the excess acid of estimating subsequently.Calculating for the first time is to estimate excessive acid, and supposition at this moment: 1) copper, iron and molybdenum dissolve fully in the enriched material material; 2) 30% iron precipitates, and comprises recycle and dissolved iron from enriched material; 3) all the molybdenum of recycle adds that the molybdenum of dissolved 20% from enriched material precipitates.30% iron sludge number is to separate out the mean value of experiment when carrying out for 200-220 ℃.Under higher temperature, have more iron precipitation.Can dope with model under the situation of high molybdenum solubleness, select 20% molybdenum, be for fear of handling big negative value.This excessive acid number adds that the correction value to the dissolved iron of estimating is used for calculating the initial predicted value of solvable molybdenum.Proofread and correct excessive acid number then,, make last prediction again with the extra precipitation capacity of compensation molybdenum.Fig. 5 has compared the solvable molybdenum concentration and actual solvable molybdenum concentration with model prediction.Notice that if model is very perfect, then all points all will drop on the straight line of drawing according to experimental data.According to the fluctuation of appearance point on the straight line of model prediction, may be that experimental error and analytical error cause.
The main benefit of understanding process chemistry is to control related chemical reaction, and predicts the amount of solvable molybdenum in the autoclave ejecta.But, this understanding also helps to improve other processes, and as when the free acid in the autoclave is controlled at higher level, the level of dissolves silicon is lower.Another improvements that the present invention finds are, recycle contain free acid and iron ion separate out slurries the time, can increase the original speed of reaction, make that the required retention time of precipitation process is shorter, thereby reduced the size of processing unit.
Embodiment
Further set forth the present invention in conjunction with more following non-limiting examples now.Separate out research with in batches-continuous or batchwise process carries out.In batches-and successive processes can simulate continuous autoclave process better, and speed of response is also very fast.As long as the retention time sufficiently long is with coming to the same thing that batchwise process obtains.
1. pack in the 2 liters of Parr reactors slurries (being generally 1 liter) of preset vol are heated to used temperature under oxygen superpressure condition, separated out 30 minutes.When using the oxygen of continuous flow, foaming is a problem.Therefore, designed such program, every mistake just was at half the oxygen excess pressure drop in 15 minutes, increased oxygen then until reaching required superpressure.This can make any foam of formation come back in the slurries.If impeller on the use dip-tube then might add continuously oxygen and to steam chamber emptying.
2. discharge the slurries (slurries A) of half volume, and change fresh slurries.
3. separated out 30 minutes.
4. discharge the slurries (slurries B) of half volume, and change fresh slurries.
5. separated out 30 minutes.
6. discharge the slurries (slurries C) of half volume, and change fresh slurries.
7. separated out 30 minutes, and took out aliquot slurries (slurries D) then and be used for analyzing.
8. separated out again 30 minutes, and took out aliquot slurries (slurries E) then and be used for analyzing.
9. separated out again 30 minutes, and took out aliquot slurries (slurries F) then and be used for analyzing cooling reactor.Filter and washing solid (slurries G).
10. 35 ℃ of stirred in water bath at least 120 minutes, make middle samples all in the autoclave and finally discharge the sample ageing.This can make sample be issued to balance in the condition of the actual employing of factory.After ageing reaches balance, filter all samples, and wash with water.With filtrate and washing lotion combined analysis.Most of final sample all after filtration, washing, again pulping, refilter and washing again, to reduce the solvable vitriol of carrying secretly in the filter cake as far as possible.
11. the main ingredient of final filtrate and some trace elements in the analysis autoclave.To be divided into two or be divided into littler part through the acid residue of washing, a partial desiccation and analyzing wherein, second half separates out operation with sodium carbonate solution.
12. separate out washed residue at 50 ℃ with 18% sodium carbonate solution, dissolve remaining oxidation state molybdenum and sedimentary vitriol.Analyze sulfide remaining in the yellow soda ash residue and total (not dissolving) molybdenum.
In 2 liters and 2 gallons of Parr reactors, separate out experiment in batches.In reactor, make the enriched material pulping with circulate soln and water.Sealed reactor is depressed intensification at oxygen, and reactor was kept 150 minutes down temperature required.When with 2 liters of reactors, the dividing potential drop of control oxygen in precipitation process, method is per superpressure that reduced half in 15 minutes, adds oxygen then until reaching required superpressure.If impeller on the use dip-tube then might add oxygen and emptying steam chamber continuously.When the reactor that uses 2 gallons, bubbling is not problem, at this moment can add oxygen and emptying steam chamber continuously continuously.
Table 1 has compared prediction and actual solvable molybdenum value when experimentizing with four samples.
Embodiment 3 low Mo solubility conditions are to the influence of solvable silicon
With low molybdenum solubleness is in the experiment of target, and the silicon value of lye is more much lower than the viewed value of early stage experiment of acid control of no use.Below table 2 compared observed silico analysis scope in the silico analysis result of these low molybdenum solubility tests and all tests.The silicon value is low may be since in autoclave recycle the lye of high acid content and low silicon content, for example balance is separated out charging.
Table 1 utilizes separates out the embodiment that model produces the high and reaction under high pressure product that molybdenum solubleness is low of molybdenum solubleness
| Enriched material 1 | Enriched material 2 | Enriched material 3 | Enriched material 4 | |||||
| Enriched material is analyzed | ||||||||
| Copper, % | 3.8 | 2.1 | 2.0 | 7.2 | ||||
| Molybdenum, % | 12.8 | 22.3 | 22.8 | 26.9 | ||||
| Iron, % | 4.0 | 2.3 | 2.2 | 6.9 | ||||
| Sulphur, % | 12.4 | 17.2 | 18.1 | 25.8 | ||||
| Target molybdenum solubleness | High | Low | High | Low | High | Low | High | Low |
| Test number | 134 | 102 | 43 | 109 | 137 | 70 | 47 | 67 |
| Separate out charging | ||||||||
| Enriched material, gram | 184 | 230 | 119 | 140 | 141 | 179 | 96 | 96 |
| Circulation copper, mol/mol Mo | 0.00 | 0.2 | 0.00 | 0.12 | 0.42 | 0.04 | 0.00 | 0.23 |
| Circulation iron, mol/mol Mo | 0.39 | 0.22 | 0.79 | 0.13 | 0.5 | 0.17 | 0.57 | 0.56 |
| Circulation or the H that adds by titration 2SO 4，mol/mol Mo | 0.43 | 1.94 | 0.46 | 1.48 | 2.72 | 0.71 | 0.47 | 5.2 |
| Excessive H 2SO 4，mol/mol Mo | -0.0 4 | 0.52 | -0.3 1 | 0.41 | 0.41 | 0.21 | -0.2 3 | 1.34 |
| The autoclave ejecta | ||||||||
| Prediction g/l Mo | 23.8 | 10.3 | 25.4 | 7.3 | 13.4 | 8.4 | 26.2 | 9.6 |
| Actual g/l Mo | 27.3 | 10.1 | 28.5 | 6.3 | 19.1 | 10.1 | 25.6 | 14.1 |
| Actual g/l Cu | 7.1 | 16.6 | 2.6 | 5.6 | 10.8 | 5.1 | 6.8 | 13.2 |
| Actual g/l Fe | 11.6 | 11.7 | 14 | 5.1 | 12.5 | 7.6 | 13 | 17.1 |
| Titrating free H 2SO 4，g/l | 77 | 144 | 90 | 117 | 29 | 93 | 85 | 158 |
| Excessive H 2SO 4，g/l | -20 | 67 | -9 | 82 | 1 | 45 | -12 | 64 |
| Residue is analyzed | ||||||||
| Sulphur, %, Na 2CO 3After separating out | 0.61 | 0.02 | 0.41 | 0.27 | 0.36 | 0.1 | 0.49 | 0.1 |
| Molybdenum, % | 0.3 | 16 | 2.2 | 28.6 | 5.9 | 25 | 1.7 | 41.4 |
| Molybdenum, %, Na 2CO 3After separating out | 0.15 | 0.04 | 0.1 | 0.43 | 0.6 | 0.17 | 0.5 | 0.3 |
| Precipitation efficiency | ||||||||
| The oxidation of sulfide, % | 99 | 96.8 | 96.5 | 98.6 | 97.5 | 99.5 | 98.3 | 99.9 |
| Solvable molybdenum in the lye, % | 98.8 | 9 | 92 | 10 | 75 | 21 | 95 | 10 |
| The molybdenum of total oxidation, % | 99.9 | 99 | 99.8 | 99 | 98 | 99.7 | 98.5 | 99.4 |
Table 2
| Enriched material | Enriched | |
| Molybdenum (g/l) | 9.9 | 9.3 |
| Solvable molybdenum (%) | 11 | 16 |
| Silicon (mg/l) | 64 | 96 |
Claims (9)
1. the method for a pressure oxidation of molybdenite enriched material, it comprises:
A. in the presence of sulfuric acid and/or hydrogen sulfate ion, form the water-soluble serous of described molybdenum glance enriched material;
B. heat described slurries at least 200 ℃;
C. with the atmosphere contact conditions that contains free oxygen under stir described slurries;
D. be at least the described slurries of oxidation in the described atmosphere of 50p.s.i. at oxygen pressure;
E. predict the concentration of dissolved molybdenum in the high-pressure oxidation process, comprising:
Measure the molar weight of Mo, Cu and Fe in every liter of enriched material, represent with A, B and C respectively; Value calculating according to measured A, B and C is measured H only from the vitriolic of enriched material, and unit is mol/l, and calculation formula is " (B*3)-((C-B) * 0.5)+(A*0.2*2)+(C*0.3*3) ";
Measure Mo, Cu in every liter of circulate soln, Fe and vitriolic molar weight, represent with D, E, F and G respectively; Calculate the amount I of excess sulfuric acid according to the value of measured D, E, F and G, unit is mol/l, and calculation formula is " G+ ((3*D)-(2*E)-(3*F))/2 "; And according to the initial total amount J of this I value calculating vitriolic, unit is mol/l, and calculation formula is " I+H ";
Calculate the Fe concentration K of prediction according to formula " ((C*0.7)+F) * 55.85 ", unit is g/l;
Calculate the tentative prediction concentration L of Mo then, unit is g/l, calculation formula be " (10.369* (J^3))+(38.992* (J^2))+(46.065*J)+25.892+ (K/3)-3.3 ";
According to the total amount Q of formula " I+C+P " calculating excess sulfuric acid, unit is mol/l; Wherein P represents from extra sedimentary vitriolic amount, in mol/l, calculates according to formula " (O-0.2) * (A*4/2) "; O represents to precipitate percentage ratio, calculates with " N/M "; And M represents if all MoS
2Solvable, the concentration in g/l of Mo is calculated according to formula " 96*A "; N represents to precipitate MoS
2In the concentration of Mo, in g/l, calculate according to formula " M-L ";
Calculate the final prediction concentrations R of Mo, in g/l, calculation formula is " (10.369* (Q^3))+(38.992* (Q^2))-(46.065*Q)+25.892+ (K/3)-3.3 ";
If R greater than M, then counts dissolved molybdenum concentration S with M; If R less than M, then counts S with R;
Wherein, " * " expression is taken advantage of, and "/" expression removes, and " ^ " represents power;
F. in oxidation reaction process, regulate ferric iron concentration and excess sulfuric acid concentration;
G. produce thus and separate out slurries, the molybdenum above 99% in the wherein said molybdenum glance enriched material obtains oxidation.
2. the described method of claim 1 is characterized in that being lower than 20% or to surpass 80% described molybdenum through oxidation be soluble.
3. the described method of claim 1 is characterized in that described molybdenum glance enriched material comprises copper, and copper surpasses 99% at described meltage of separating out in the slurries.
4. the described method of claim 1 it is characterized in that described molybdenum glance enriched material comprises iron, and iron is 60%-90 weight % at described meltage of separating out in the slurries.
5. the described method of claim 1 is characterized in that regulating step makes that sulfuric acid maintains higher excessive concentrations in the described slurries, in order to produce low solvable silicone content.
6. the described method of claim 1 is characterized in that regulating step makes that ferric iron maintains higher concentration in the described slurries, in order to accelerate oxidizing reaction speed.
7. the described method of claim 1 is characterized in that it also comprises the described slurries of separating out of a part that produces in the step (g) are turned back to and form in the step (a), as circulate soln.
8. the described method of claim 1 is characterized in that oxygen overpressure in the oxidation step is in the 80-120p.s.i. scope.
9. the described method of claim 1, the temperature that it is characterized in that heating steps is in 210-220 ℃ of scope.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/851,920 | 2001-05-09 | ||
| US09/851,920 US6818191B2 (en) | 2001-05-09 | 2001-05-09 | Autoclave control mechanisms for pressure oxidation of molybdenite |
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| Publication Number | Publication Date |
|---|---|
| CN1531508A CN1531508A (en) | 2004-09-22 |
| CN1300003C true CN1300003C (en) | 2007-02-14 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB018232434A Expired - Fee Related CN1300003C (en) | 2001-05-09 | 2001-09-26 | Autoclave control method for pressure oxidation of molybdenite |
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| Country | Link |
|---|---|
| US (1) | US6818191B2 (en) |
| EP (1) | EP1390299B1 (en) |
| JP (1) | JP2005507457A (en) |
| KR (1) | KR20040005949A (en) |
| CN (1) | CN1300003C (en) |
| AT (1) | ATE443029T1 (en) |
| CA (1) | CA2449185C (en) |
| DE (1) | DE60139960D1 (en) |
| MX (1) | MXPA03010123A (en) |
| PE (1) | PE20021127A1 (en) |
| RU (1) | RU2304560C2 (en) |
| TW (1) | TW593157B (en) |
| WO (1) | WO2002090263A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008061231A1 (en) * | 2006-11-16 | 2008-05-22 | Albemarle Netherlands B.V | Purification of molybdenum technical oxide |
| JP2010510156A (en) * | 2006-11-16 | 2010-04-02 | アルベマール・ネーザーランズ・ベーブイ | Industrial molybdenum oxide purified from molybdate |
| WO2013142022A1 (en) | 2012-03-23 | 2013-09-26 | Kennecott Utah Copper Llc | Process for the conversion of molybdenite to molybdenum oxide |
| CN103014331A (en) * | 2013-01-16 | 2013-04-03 | 四川顺应金属材料科技有限公司 | Process for pressure leaching of molybdenum and nickel from molybdenum-nickel ore |
| KR20150064258A (en) * | 2013-11-28 | 2015-06-11 | 한국지질자원연구원 | Method of treating molybdenite containing copper |
| JP6196209B2 (en) * | 2014-12-10 | 2017-09-13 | Ｊｘ金属株式会社 | Method for treating copper-containing molybdenum ore |
| WO2015199098A1 (en) * | 2014-06-25 | 2015-12-30 | Jx日鉱日石金属株式会社 | Method for processing copper-containing molybdenum ore |
| PE20230978A1 (en) * | 2015-11-12 | 2023-06-19 | Jx Nippon Mining & Metals Corp | METHOD TO SEPARATE MOLYBDENUM AND METHOD TO TREAT MOLYBDENUM CONCENTRATE CONTAINING COPPER |
| TWI731678B (en) * | 2020-05-12 | 2021-06-21 | 中宇環保工程股份有限公司 | Method and device for treating molybdenum-containing wastewater and recovering iron molybdate crystals |
| CN115305363B (en) * | 2022-08-16 | 2023-10-20 | 紫金矿业集团股份有限公司 | Method for efficiently oxidizing molybdenite in sulfuric acid and ferric sulfate solution under normal pressure |
| CN116043038A (en) * | 2023-02-10 | 2023-05-02 | 东北大学 | Low-grade tungsten-molybdenum ore synergistic oxidation leaching method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3656888A (en) * | 1969-10-02 | 1972-04-18 | American Metal Climax Inc | Liquid phase oxidation process |
| US4512958A (en) * | 1983-10-28 | 1985-04-23 | Gfe Gesellschaft Fur Elektrometallurgie Mbh | Method of recovering molybdenum oxide |
| US5804151A (en) * | 1997-09-16 | 1998-09-08 | Cyprus Amax Minerals Company | Process for autoclaving molybdenum disulfide |
-
2001
- 2001-05-09 US US09/851,920 patent/US6818191B2/en not_active Expired - Fee Related
- 2001-09-26 DE DE60139960T patent/DE60139960D1/en not_active Expired - Lifetime
- 2001-09-26 CN CNB018232434A patent/CN1300003C/en not_active Expired - Fee Related
- 2001-09-26 EP EP01977180A patent/EP1390299B1/en not_active Expired - Lifetime
- 2001-09-26 JP JP2002587349A patent/JP2005507457A/en active Pending
- 2001-09-26 MX MXPA03010123A patent/MXPA03010123A/en active IP Right Grant
- 2001-09-26 RU RU2003135791A patent/RU2304560C2/en not_active IP Right Cessation
- 2001-09-26 KR KR10-2003-7014550A patent/KR20040005949A/en not_active Application Discontinuation
- 2001-09-26 WO PCT/US2001/030059 patent/WO2002090263A1/en active Application Filing
- 2001-09-26 AT AT01977180T patent/ATE443029T1/en not_active IP Right Cessation
- 2001-09-26 CA CA 2449185 patent/CA2449185C/en not_active Expired - Fee Related
-
2002
- 2002-05-09 TW TW91110107A patent/TW593157B/en not_active IP Right Cessation
- 2002-05-09 PE PE2002000387A patent/PE20021127A1/en not_active Application Discontinuation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3656888A (en) * | 1969-10-02 | 1972-04-18 | American Metal Climax Inc | Liquid phase oxidation process |
| US4512958A (en) * | 1983-10-28 | 1985-04-23 | Gfe Gesellschaft Fur Elektrometallurgie Mbh | Method of recovering molybdenum oxide |
| US5804151A (en) * | 1997-09-16 | 1998-09-08 | Cyprus Amax Minerals Company | Process for autoclaving molybdenum disulfide |
Also Published As
| Publication number | Publication date |
|---|---|
| US6818191B2 (en) | 2004-11-16 |
| PE20021127A1 (en) | 2003-01-15 |
| EP1390299A4 (en) | 2005-06-01 |
| US20030031614A1 (en) | 2003-02-13 |
| CA2449185A1 (en) | 2002-11-14 |
| CA2449185C (en) | 2011-03-15 |
| EP1390299A1 (en) | 2004-02-25 |
| EP1390299B1 (en) | 2009-09-16 |
| ATE443029T1 (en) | 2009-10-15 |
| CN1531508A (en) | 2004-09-22 |
| JP2005507457A (en) | 2005-03-17 |
| RU2003135791A (en) | 2005-05-20 |
| MXPA03010123A (en) | 2004-05-12 |
| WO2002090263A1 (en) | 2002-11-14 |
| DE60139960D1 (en) | 2009-10-29 |
| TW593157B (en) | 2004-06-21 |
| RU2304560C2 (en) | 2007-08-20 |
| KR20040005949A (en) | 2004-01-16 |
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